EP3626841B1 - High strength micro alloyed steel seamless pipe for sour service and high toughness applications - Google Patents

High strength micro alloyed steel seamless pipe for sour service and high toughness applications Download PDF

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Publication number
EP3626841B1
EP3626841B1 EP18195795.2A EP18195795A EP3626841B1 EP 3626841 B1 EP3626841 B1 EP 3626841B1 EP 18195795 A EP18195795 A EP 18195795A EP 3626841 B1 EP3626841 B1 EP 3626841B1
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Prior art keywords
chemical composition
weight
steel
relative
total weight
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German (de)
English (en)
French (fr)
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EP3626841A1 (en
Inventor
TRINDADE FILHO Vicente Braz DA
E Silva Julio Marcio Silveira
VILAS BÔAS Ana Carolina CALDAS
Cédric LINNE
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Vallourec Tubes France SAS
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Vallourec Tubes France SAS
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Priority to EP18195795.2A priority Critical patent/EP3626841B1/en
Priority to ES18195795T priority patent/ES2906376T3/es
Priority to PL18195795T priority patent/PL3626841T3/pl
Priority to AU2019222820A priority patent/AU2019222820B2/en
Priority to BR102019018917-7A priority patent/BR102019018917B1/pt
Priority to US16/572,918 priority patent/US12276014B2/en
Publication of EP3626841A1 publication Critical patent/EP3626841A1/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18—Hardening; Quenching with or without subsequent tempering
    • C21D1/25—Hardening, combined with annealing between 300 degrees Celsius and 600 degrees Celsius, i.e. heat refining ("Vergüten")
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/62—Quenching devices
    • C21D1/63—Quenching devices for bath quenching
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/10—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/08—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
    • C21D9/085—Cooling or quenching
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L9/00—Rigid pipes
    • F16L9/02—Rigid pipes of metal

Definitions

  • the present invention relates to micro alloyed steels with a yield strength of at least 485 MPa (70 ksi), and preferably of at least 555 MPa (80 ksi) with outstanding toughness behavior, good weldability and improved sulphide stress cracking resistance.
  • Pipes of the invention comply with tensile requirements of grades X70 and X80 according with American Petroleum Institute standard API 5L, with sulfide stress corrosion (SSC) and hydrogen induced cracking (HIC) resistance.
  • CN102154593 discloses an X80 steel grade anti-corrosion low-temperature seamless line pipe which comprises the following components in percentage by weight: 0.08 to 0.14 percent of C, 0.20 to 0.35 percent of Si, 1.10 to 1.40 percent of Mn, less than or equal to 0.015 percent of P, less than or equal to 0.005 percent of S, 0.10 to 0.20 percent of Mo, 0.020 to 0.060 percent of A1, 0.02 to 0.05 percent of Nb, 0.05 to 0.10 percent of V, 0.10 to 0.20 percent of Cu, 0.10 to 0.20 percent of Ni, less than or equal to 0.015 percent of Ti, less than or equal to 0.15 percent of Cr, 0.0015 to 0.0060 percent of Ca, less than or equal to 0.0005 percent of B, less than or equal to 0.012 percent of N, less than or equal to 0.43 percent of CEV, less than or equal to 0.23 percent of Pcm and Fe and impurity elements.
  • Line pipes used for transporting oil & gas have increased in strength every year in order to improve the project efficiency and at the same time decreasing investment costs. Additionally, requirement for high deformability and enhanced weldability are continuous demanded.
  • An objective of the invention is to propose robust steel grades that fulfill the above requirements.
  • the invention proposes steel grades according to DNV 555 SP ("X80QOS") for sour service application within Class 3 domain.
  • the present invention also relates to tubular products, such as tubes or pipes, preferably seamless pipes, made from said steel, as well as a process for manufacturing such tubular products.
  • seamless pipes for line pipes for applications as process pipes, flowlines or risers in the oil and gas industry.
  • seamless pipes according to the invention allow reduced pipe wall thickness without any disadvantage in terms of the overall material performance under severe applications.
  • Harsher environment applications had encouraged a search for accessories made of steels having good and stable mechanical properties and a satisfying toughness behavior at low temperatures, especially where high imposed strains can take place at cryogenic service temperatures down to -60°C or even down to -80°C.
  • Micro-alloying elements such as titanium, niobium and vanadium, are, generally speaking, employed to increase the strength.
  • Titanium can already partially precipitate at high temperatures in the liquid phase forming very coarse titanium nitride.
  • Niobium forms niobium (C, N) precipitates at lower temperatures.
  • vanadium carbides and nitrides are also formed.
  • H2S hydrogen sulphide
  • SSC sulphide stress cracking
  • Sulphide stress cracking resistance is thus of particular importance for oil companies since it is relevant to the safety of equipment.
  • offshore pipeline installation can be performed by reel-laying.
  • the process of reeling on and off the reel drum does lead to significant plastic deformation of the pipes. Indeed, during reel-laying, repeated plastic strain is generated into the pipeline, which may affect strength and ductility of the line pipe material and alters its corrosion resistance, especially in presence of hydrogen sulphide.
  • the steel should allow the manufacture of seamless pipes that can be used as line pipes, for applications like process pipes, flowlines or risers in the oil and gas industry.
  • the steel should also present excellent impact properties at service temperatures down to -60°C (in transversal directions) across the entire wall thickness of the pipe.
  • the steel of the present invention may present a yield strength preferably greater than or equal to 485 MPa, and lower than or equal to 695 MPa, preferably between 495 and 675 MPa.
  • steel's yield strength is greater than or equal to 555 MPa and lower than or equal to 705 MPa, in order to comply with grade X80 of API, and preferably steel's yield strength is lower than or equal to 675 MPa, in order to fulfill DNV GL ST-F101 standards.
  • the yield strength is determined by tensile tests as defined in standards ASTM A370-17 and ASTM E8/E8M-13a.
  • the steel of the present invention exhibits outstanding hardness and toughness behavior, especially under stringent conditions, namely in presence of a corrosive media. Indeed, the steel of the invention presents excellent mechanical properties and a high toughness at temperatures even down to -80°C, as well as an improved sulphide stress cracking resistance.
  • the steel of the present invention can particularly be used in tubular products, preferably seamless pipes, exhibiting uniform hardness throughout their wall thickness, even for thinner wall thickness.
  • the steel of the present invention is able to lead to seamless pipes having high yield and tensile strengths, a high strain capacity, a low and uniform hardness, namely throughout their entire length and wall thickness, and exhibiting a high and steady toughness performance, while presenting an excellent SSC resistance.
  • the steel of the present invention is able to lead to seamless pipes displaying high and steady toughness performance, even after being strained and aged, while still presenting an excellent SSC resistance.
  • the seamless pipes made from the steel of the invention can still be used efficiently under harsh conditions even after undergoing a plastic deformation.
  • seamless pipes made from the steel of the invention are able to display good and stable mechanical properties during reel-laying.
  • Another object of the present invention concerns a seamless pipe made from a steel as previously defined.
  • the present invention also relates to a process for manufacturing a seamless pipe comprising the following successive steps:
  • the seamless pipe thus obtained from the steel of the invention presents an improved sulphide stress cracking resistance.
  • the tubular product and notably the steel seamless pipes are particularly suitable for demanding environments. These demanding environments may incorporate a combination of very challenging factors including, for example, deep-water locations, increased pressure and temperature wells, more corrosive products, and lower design temperatures. These conditions, when added to stringent weldability and toughness criteria already associated with pipe specifications for offshore oil and gas exploration applications, place ever increasing demands on the materials and supply capability.
  • This product presents the advantages of having good and stable mechanical properties throughout its length and wall thickness, which is the distinction of a substantially uniform microstructure, as well as an excellent SSC resistance.
  • the present invention also relates to the use of such a seamless pipe for line pipes, for applications as process pipes,flowlines or risers in the oil and gas industry.
  • the chemical composition of the steel according to the present invention contains 0.05 ⁇ C ⁇ 0.10% by weight, relative to the total weight of said chemical composition.
  • the chemical composition of the steel contains carbon (C) in a content ranging from 0.05 to 0.10% by weight, relative to the total weight of said chemical composition; it being understood that both lower (0.05% by weight) and higher (0.10% by weight) limits being included.
  • the objective is to achieve high strength and at the same time low hardness and high toughness. Below 0.05% by weight, the tensile strength decreases significantly and there is a risk to have yield strength below expectation.
  • the content of carbon has to be higher than or equal to 0.05% by weight in order to ensure grade X70 and/or X80 strengths in case of quenched and tempered seamless pipes
  • the carbon content is preferably higher than or equal to 0.06% (0.06% ⁇ C) by weight, relative to the total weight of the chemical composition.
  • the carbon content is preferably lower than or equal 0.08% (C ⁇ 0.08%) by weight, relative to the total weight of the chemical composition.
  • the carbon content preferably ranges from 0.06 to 0.08% by weight, relative to the total weight of the chemical composition.
  • the chemical composition of the steel according to the present invention preferably contains 0.06 ⁇ C ⁇ 0.08% by weight, relative to the total weight of said chemical composition.
  • the chemical composition of the steel according to the present invention further contains 0.15 ⁇ Si ⁇ 0.35% by weight, relative to the total weight of said chemical composition.
  • the chemical composition of the steel contains silicon (Si) in a content ranging from 0.15% to 0.35% by weight, relative to the total weight of said chemical composition; it being understood that both lower (0.15% by weight) and higher (0.35% by weight) limits being included.
  • This element is used as deoxidizer in liquid state and this effect is more effectively obtained with contents above 0.15% by weight. Such contents also increase strength of the steel, especially the ultimate tensile strength, improving the yield ratio (YS/UTS). However, above 0.35% by weight, the toughness of the steel is negatively affected and decreases.
  • Silicon is also needed to retard softening phenomenon during high temperature tempering and also the derating of the tensile properties of the steel.
  • the silicon content is preferably higher than or equal to 0.23% (0.23% ⁇ Si) by weight, and more preferably higher than or equal to 0.26% (0.26% ⁇ Si) by weight relative to the total weight of the chemical composition.
  • the silicon content is preferably lower than or equal to 0.31% (Si ⁇ 0.31%) by weight, and more preferentially lower than or equal to 30% (Si ⁇ 0.30%) by weight, relative to the total weight of the chemical composition.
  • the silicon content preferably ranges from 0.23 to 0.31% by weight, and more preferentially from 0.26 to 0.30% by weight, relative to the total weight of the chemical composition.
  • the chemical composition of the steel according to the present invention preferably contains 0.23 ⁇ Si ⁇ 0.31% by weight, and more preferentially 0.26 ⁇ Si ⁇ 0.30% by weight, relative to the total weight of said chemical composition.
  • the chemical composition of the steel according to the present invention further contains 1.20 ⁇ Mn ⁇ 1.50% by weight, relative to the total weight of said chemical composition.
  • the chemical composition of the steel contains manganese (Mn) in a content ranging from 1.20 to 1.50% by weight, relative to the total weight of said chemical composition; it being understood that both lower (1.20% by weight) and higher (1.50% by weight) limits being included.
  • the manganese content is preferably higher than or equal to 1.35% (1.35% ⁇ Mn) by weight, and more preferentially 1.40% (1.40% ⁇ Mn) by weight relative to the total weight of the chemical composition.
  • the manganese content is preferably lower than or equal to 1.45% (Mn ⁇ 1.45%) by weight, relative to the total weight of the chemical composition.
  • the manganese content preferably ranges from 1.35 to 1.45% by weight, and more preferentially from 1.40 to 1.45% by weight, relative to the total weight of the chemical composition.
  • the chemical composition of the steel according to the present invention preferably contains 1.35 ⁇ Mn ⁇ 1.45% by weight, and more preferentially 1.40 ⁇ Mn ⁇ 1.45% by weight relative to the total weight of said chemical composition.
  • the chemical composition of the steel according to the present invention further contains 0.02 ⁇ Cr ⁇ 0.10% by weight, relative to the total weight of said chemical composition.
  • the chemical composition of the steel contains chromium (Cr) in a content ranging from 0.02 to 0.10% by weight, relative to the total weight of said chemical composition; it being understood that both lower (0.02% by weight) and higher (0.10% by weight) limits being included.
  • Chromium improves the hardenability of the steel leading to enhancement of the tensile strengths. But higher content can be deleterious to the weldability of the steels due to increasing on hardness and decreasing the toughness.
  • the content of chromium has to remain lower than or equal to 0.10% by weight in order to avoid any hard spots (high local hardness spots) during tempering and/or during welding caused by the formation and the precipitation of carbides. Such precipitates are indeed detrimental to SSC.
  • the chromium content is preferably higher than or equal to 0.06% (0.06% ⁇ Cr) by weight, relative to the total weight of the chemical composition.
  • the chromium content is preferably lower than or equal to 0.08% (Cr ⁇ 0.08%) by weight, relative to the total weight of the chemical composition.
  • the chromium content preferably ranges from 0.06 to 0.08% by weight, relative to the total weight of the chemical composition.
  • the chemical composition of the steel according to the present invention preferably contains 0.06 ⁇ Cr ⁇ 0.08% by weight, relative to the total weight of said chemical composition.
  • the chemical composition of the steel according to the present invention further contains 0.10 ⁇ Mo ⁇ 0.30% by weight, relative to the total weight of said chemical composition.
  • the chemical composition of the steel contains molybdenum (Mo) in a content ranging from 0.10 to 0.30% by weight, relative to the total weight of said chemical composition; it being understood that both lower (0.10% by weight) and higher (0.30% by weight) limits being included.
  • Molybdenum increases both yield and tensile strengths and supports the homogeneity of the mechanical properties, the microstructure and the toughness of the steel along the whole length and thickness of the seamless pipe.
  • the presence of molybdenum also makes possible to increase the tempering temperature and to provide thicker seamless pipes, without changing other process parameters, improving thus the hardness of said seamless pipe, as well as its SSC resistance.
  • Molybdenum also increases the hardenability of the steel.
  • the molybdenum content is preferably higher than or equal to 0.16% (0.16% ⁇ Mo) by weight, and more preferentially higher than or equal to 0.20% (0.20% ⁇ Mo) by weight, relative to the total weight of the chemical composition.
  • the molybdenum content is preferably lower than or equal to 0.26% (Mo ⁇ 0.26%) by weight, and more preferably lower than or equal to 0.24% (Mo ⁇ 0.24%) by weight relative to the total weight of the chemical composition.
  • the molybdenum content preferably ranges from 0.16 to 0.26% by weight, more preferentially from 0.20 to 0.24% by weight relative to the total weight of the steel.
  • the chemical composition of the steel according to the present invention preferably contains 0.16 ⁇ Mo ⁇ 0.26% by weight, more preferentially 0.20 ⁇ Mo ⁇ 0.24% by weight relative to the total weight of said chemical composition.
  • the chemical composition of the steel according to the present invention preferably satisfies the following formula (2) between Cr and Mo, the contents of which are expressed in weight%, Cr + Mo ⁇ 0.35 %
  • the sum of Cr and Mo contents is preferably lower than or equal to 0.35% by weight, relative to the total weight of the steel.
  • Higher value of these elements combination can cause very high strength combined with undesirable high hardness. Therefore, a very high tempering temperature might be necessary causing recrystallization of the martensite laths formed near to the pipe surfaces during the quenching process.
  • too lower tempering temperature can drive to undesirable too high values for hardness and/or tensile strength.
  • the chemical composition of the steel according to the present invention further contains 0.015 ⁇ Al ⁇ 0.040% by weight, relative to the total weight of said chemical composition.
  • the chemical composition of the steel contains aluminum (Al) in a content ranging from 0.015 to 0.040% by weight, relative to the total weight of said chemical composition; it being understood that both lower (0.015% by weight) and higher (0.040% by weight) limits being included.
  • Aluminum is a powerful steel deoxidizer and grain refiner.
  • the content of aluminum should not exceed 0.040% by weight because the cleanliness of the steel can be negatively affected by a potential stronger formation of aluminum oxides.
  • too low value of Al is also not desirable due to the necessary deoxidation of the steel as well as because of the necessity of a reasonable amount of AlN in order to inhibit the grain growth during rolling, heat treatment and welding operations.
  • the aluminum content is preferably higher than or equal to 0.20% (0.20% ⁇ Al) by weight, relative to the total weight of the chemical composition.
  • the aluminum content is preferably lower than or equal to 0.35% (Al ⁇ 0.35%) by weight, relative to the total weight of the chemical composition.
  • the aluminum content preferably ranges from 0.20 to 0.35% by weight, relative to the total weight of the steel.
  • the chemical composition of the steel according to the present invention preferably contains 0.20 ⁇ Al ⁇ 0.35% by weight, relative to the total weight of said chemical composition.
  • the chemical composition of the steel according to the present invention further contains 0.002 ⁇ N ⁇ 0.012% by weight, relative to the total weight of said chemical composition.
  • the chemical composition of the steel contains nitrogen (N) in a content ranging from 0.002 to 0.012% by weight, relative to the total weight of said chemical composition; it being understood that both lower (0.002% by weight) and higher (0.012% by weight) limits being included.
  • nitrogen forms coarse carbo-nitrides that negatively affect the toughness and it is also deleterious to SSC resistance. Additionally, too high nitrogen can also accelerate the strain ageing of steel pipes that are undertaken to plastic deformation during reel laying process. On the other hand, too lower content of nitrogen is also deleterious due to the reduction of the precipitation of the carbonitrides and/or aluminum nitrides that are necessary for grain growth inhibition, and to increase the tensile properties.
  • the nitrogen content is preferably higher than or equal to 0.005% (0.005% ⁇ N) by weight, relative to the total weight of the chemical composition.
  • the nitrogen content is preferably lower than or equal to 0.10% (N ⁇ 0.10%) by weight, relative to the total weight of the chemical composition.
  • the nitrogen content preferably ranges from 0.005 to 0.10% by weight, relative to the total weight of the steel.
  • the chemical composition of the steel according to the present invention preferably contains 0.005 ⁇ N ⁇ 0.10% by weight, relative to the total weight of said chemical composition.
  • the chemical composition of the steel according to the present invention further contains 0.10 ⁇ Ni ⁇ 0.30% by weight, relative to the total weight of said chemical composition.
  • the chemical composition of the steel contains nickel (Ni) in a content ranging from 0.10 to 0.30% by weight, relative to the total weight of said chemical composition; it being understood that both lower (0.10% by weight) and higher (0.30% by weight) limits being included.
  • Nickel improves the steel hardness. It increases yield strength, as well as tensile strength. Nickel is a very important element to improve the toughness, especially at very low temperatures.
  • the nickel content is preferably higher than or equal to 0.12% (0.12% ⁇ Ni) by weight, relative to the total weight of the chemical composition.
  • the nickel content is preferably lower than or equal to 0.20% (Ni ⁇ 0.20%) by weight, relative to the total weight of the chemical composition.
  • the nickel content preferably ranges from 0.12 to 0.20% by weight, relative to the total weight of the steel.
  • the chemical composition of the steel according to the present invention preferably contains 0.12 ⁇ Ni ⁇ 0.20% by weight, relative to the total weight of said chemical composition.
  • the chemical composition of the steel according to the present invention further contains 0.02 ⁇ V ⁇ 0.06% by weight, relative to the total weight of said chemical composition.
  • the chemical composition of the steel contains vanadium (V) in a content ranging from 0.02 to 0.06% by weight, relative to the total weight of said chemical composition; it being understood that both lower (0.02% by weight) and higher (0.06% by weight) limits being included.
  • Vanadium increases the tensile properties due to precipitation hardening phenomenon. Above 0.06% by weight, vanadium precipitates (nitrides and/or carbides) increase the risk of having peaks of hardness at Heat Affected Zone as well as a scattering in toughness values at low temperatures and/or a shift of transition temperatures to higher temperatures. Consequently, the toughness properties are negatively impacted by such contents. On the other hand, too lower content of vanadium does not increase the strength of the steels. Vanadium also has a minor effect on the hardenability of steels.
  • the vanadium content is preferably higher than or equal to 0.03% (0.03% ⁇ V) by weight, relative to the total weight of the chemical composition.
  • the vanadium content is preferably lower than or equal to 0.05% (V ⁇ 0.05%) by weight relative to the total weight of the chemical composition.
  • the vanadium content preferably ranges from 0.03 to 0.05% by weight relative to the total weight of the chemical composition.
  • the chemical composition of the steel according to the present invention preferably contains 0.03 ⁇ V ⁇ 0.05% by weight relative to the total weight of said chemical composition.
  • the chemical composition of the steel according to the present invention further contains 0.01 ⁇ Nb ⁇ 0.03% by weight, relative to the total weight of said chemical composition.
  • the chemical composition of the steel contains niobium (Nb) in a content ranging from 0.01 to 0.03% by weight, relative to the total weight of said chemical composition; it being understood that both lower (0.01% by weight) and higher (0.03% by weight) limits being included.
  • Niobium leads to carbide and/or nitride precipitates resulting into a fine grain size microstructure by grain boundary pinning effects and improved tensile strength.
  • niobium can have a negative impact in the hardness, especially at the Heat Affected Zone. And then it can also have a negative impact on the toughness through the formation of coarse precipitates.
  • the niobium content is preferably higher than or equal to 0.02% (0.02% ⁇ Nb) by weight, relative to the total weight of the chemical composition.
  • the niobium content is preferably lower than or equal to 0.028% (Nb ⁇ 0.028%) by weight relative to the total weight of the chemical composition.
  • the niobium content preferably to the total weight of the chemical composition.
  • the chemical composition of the steel according to the present invention preferably contains 0.02% ⁇ Nb ⁇ 0.028% by weight relative to the total weight of said chemical composition.
  • the chemical composition of the steel according to the present invention preferably satisfies the following formula (3) between Nb and V, the contents of which are expressed in weight%, Nb + V ⁇ 0.07
  • the sum of Nb and V contents is preferably lower than or equal to 0.07% by weight, relative to the total weight of the steel in order to avoid any hardness peak in the heat affected zone (HAZ) and to improve the SSC resistance in this region.
  • the chemical composition of the steel according to the present invention further contains 0.001% ⁇ Ti ⁇ 0,025%; by weight, relative to the total weight of said chemical composition.
  • the chemical composition of the steel contains titanium (Ti) in a content up to 0.025% by weight, relative to the total weight of said chemical composition; it being understood that upper limit is included (0.025% by weight).
  • titanium can lead to the coarse carbide and/or nitride precipitates, which drive to a poorer grain refinement control as well as to a higher susceptibility to secondary cracking on SSC tests.
  • titanium negatively affects the yield strength and the toughness of the steel.
  • the titanium content is preferably in the range of 0.005 ⁇ Ti ⁇ 0.020% by weight, relative to the total weight of the chemical composition.
  • the chemical composition of the steel according to the present invention preferably satisfies the following formula (4) between Nb, V and Ti, the contents of which are expressed in weight%, Nb + V + Ti ⁇ 0.095
  • the sum of Nb, V and Ti contents is preferably lower than or equal to 0.095% by weight, relative to the total weight of the steel.
  • This element combination is important to avoid hardness spot in the heat affected zone of girth welds, improving the SSC resistance and the toughness in this region.
  • the balance of the chemical composition of the steel according to the present invention is made of Fe and residual elements resulting from the steel production and casting processes, including P, S, B, Ca, Cu and mixtures thereof.
  • the chemical composition contains residual elements chosen from P, S, B, Ca, Cu and mixtures thereof.
  • residual elements refers to inevitable elements resulting from the steel production and casting processes.
  • the contents of the residual, expressed in weight%, relative to the total weight of said chemical composition, are preferably as follows: P ⁇ 0.012 S ⁇ 0.003 B ⁇ 0.0005 Ca ⁇ 0.004 Cu ⁇ 0.12
  • the boron (B) content is preferably lower than or equal to 0.0005% by weight, relative to the total weight of the chemical composition of the steel. Above this content, boron can negatively impact the weldability due to hard spots formation at the Heat Affected Zone. More preferably, the steel composition is boron free. Boron free composition contains Boron less than 0.0005% by weight, relative to the total weight of the chemical composition of the steel.
  • the chemical composition of the steel according to the present invention may further contain Cu ⁇ 0.12% by weight, relative to the total weight of said chemical composition.
  • the chemical composition of the steel may further contain copper (Cu) in a content lower than or equal to 0.12% by weight, relative to the total weight of said chemical composition. Above 0.12% by weight, copper may lead to the surface defects due to the hot shortness phenomenon.
  • Ca and REM rare earth metals
  • P and S decrease SSC resistance and the toughness.
  • Carbon Equivalent and Pcm are calculated parameters in weight percent, relating the combined effects of different alloying elements in steels to an equivalent amount of carbon.
  • the desire tensile strength can be varied by changing the amount of carbon and other alloying elements by means of a proper heat treatment. These parameters are very important to enable a better weldability, toughness and tensile strength. The lower Carbon Equivalent and Pcm, the better will be the weldability and toughness. But it cannot be too low, since the minimum tensile strength will not be reached.
  • the present invention also relates to a seamless pipe, made from a steel as previously defined.
  • seamless pipe are of the X80 grade, with a steel yield strength between 555 MPa and 740 MPa, a pipe wall thickness between à 15.1 and 35 mm, and such that the steel chemical composition contains in weight%, relative to the total weight of said chemical composition: 0.16 ⁇ Mo ⁇ 0.26, and preferably 0.20 ⁇ Mo ⁇ 0.24.
  • seamless pipe are of the X70 grade, with a steel yield strength between 485 MPa and 635 MPa, a pipe wall thickness between 9,3 and 40 mm, and such that the steel chemical composition contains in weight%, relative to the total weight of said chemical composition: 0.10 ⁇ Mo ⁇ 0.21.
  • Another object of the present invention concerns a process for manufacturing a seamless pipe as previously defined.
  • a seamless pipe made from steel according to the present invention is obtained according to conventional hot forming methods.
  • the steel according to the present invention may be melted by commonly-used melting practices and commonly-used casting process such as the continuous casting or the ingot casting-blooming methods.
  • the steel is then heated to a temperature ranging from 1100 °C and 1300°C, so that at all points the temperature reached is favorable to the high rates of deformation the steel will undergo during hot forming.
  • the maximum temperature is lower than 1300°C to avoid burning. Below 1100°C, the hot ductility of the steel is negatively impacted.
  • the steel is advantageously hot formed in at least one step by rolling.
  • This tubular product presents preferably a wall thickness ranging from 9.3 to 50 mm, and more preferably from 15 to 35 mm.
  • the seamless pipe is then austenitized, i.e. heated up to an austenitization temperature (AT) to achieve a homogeneous microstructure along its length and across the wall section.
  • AT austenitization temperature
  • the seamless pipe made of steel according to the present invention is then kept at the austenitization temperature AT for an austenitization time At of at least 2 minutes, the objective being that at all points of the tube, the temperature reached is at least equal to the austenitization temperature.
  • the temperature should be homogeneous throughout the tube.
  • the austenitization time At shall not be above 60 minutes because above such duration, the austenite grains grow undesirably large and lead to a coarser final structure. This would be detrimental to toughness and SSC resistance.
  • the austenitized seamless pipe made of steel according to the present invention is then cooled to the ambient temperature, for example in water (water quench).
  • the quenched seamless pipe made of steel according to the present invention is then tempered, i.e. heated up at a tempering temperature (TT) ranging from 630 to 670°C, preferably from 630 to 665°C, and more preferentially from 635 to 660°C.
  • TT tempering temperature
  • the tempering temperature has to remain below 670°C in order to avoid any recrystallization of martensite underneath the outer and inner pipe surfaces, that would be deleterious to the SSC resistance as well as the tensile properties and fatigue resistance, but higher than 630°C to keep the homogeneous microstructure all along the seamless pipe.
  • the tempering temperature has to remain above 630°C, in order to avoid peaks of hardness at ID and OD surfaces
  • Such tempering step is done during a tempering time Tt, preferably between 20 and 60 minutes. This leads to a quenched and tempered steel seamless pipe.
  • the quenched and tempered steel seamless pipe according to the invention is then cooled down to the ambient temperature using either water or air cooling.
  • the seamless pipe thus obtained may further undergo additional finishing steps, such as sizing, coating or straightening.
  • the quenched and tempered steel seamless pipe is then useful for for line pipes, for applications as process pipes, flowlines or risers in the oil and gas industry.
  • the present invention also concerns use of a seamless pipe as previously defined for line pipes.
  • compositions of seamless pipe's steels according to the present invention (A1), (A2) and (A3) have been prepared from the elements indicated in the table 1 below, the amounts of which are expressed as percent by weight, relative to the total weight of the chemical composition.
  • Table 1 Chemical composition (Unit: mass%, Balance: Fe and residual elements) C 0.075 0.062 0.075 Si 0.273 0.277 0.298 Cr 0.062 0.065 0.078 Al 0.027 0.025 0.025 N 0.005 0.0072 0.0088 Nb 0.0215 0.0209 0.0236 Ti 0.0055 0.0052 0.0055 P 0.006 0.009 0.01 s 0.0017 0.0023 0.0019 B 0.0004 0.0004 0.0004 Ca 0.0009 0.0012 0.0015 Cu 0.029 0.05 0.04 Pcm 0.181 0.173 0.190 Ceq 0.381 0.381 0.404 Steel A1 A2 A3 C+Cr+Mo+Nb+V+Ti 0.372 0.410 0.4988 Nb+V
  • the steels (A1), (A2) and (A3) having the chemical compositions described in the table 1 above have been heated and then hot formed into seamless steel pipes of the desired dimensions by hot working using a rolling mill at 1250°C.
  • the seamless steel pipes thus obtained have a wall thickness (WT) equal to 15.9mm or 25.4mm.
  • the hardness behavior has been evaluated according to the standard ISO 6507-1.
  • Each pipe (A1, 25.4mm), (A2, 25.4mm), (A3, 25.4mm), (A1, 15.9mm) and (A2, 15.9mm) has been cut in its transversal direction and divided in four quadrants.
  • Four indentations on its outer wall, mid wall and inner wall have been performed on both bottom and head ends of the pipe. In other words, 16 measurements have been performed for each wall at the bottom end of the pipe and 16 others have been performed at the head end.
  • Each graph represents all individual values of hardness measurements performed on different positions (bottom and head ends of the pipe), as well as on cross section (outer wall, mid wall and inner wall) for each pipe (A1, 25.4mm), (A2, 25.4mm), (A3, 25.4mm), (A1, 15.9mm) and (A2, 15.9mm).
  • the tensile properties have been evaluated according to the standard ASTM A370.
  • Each graph represents the yield strength values measured for each pipe (A1, 25.4mm), (A2, 25.4mm), (A3, 25.4mm), (A1, 15.9mm) and (A2, 15.9mm).
  • the HIC test corresponding to the test according to NACE TM 0284 method, consists in immersing the test pipes in a solution (solution A) of 100% H2S. The testing duration is 96 hours. All specimens (A1, 25.4mm), (A2, 25.4mm), (A3, 25.4mm), (A1, 15.9mm) and (A2, 15.9mm) passed with no cracks, namely, crack sensitivity ratio (CSR), crack length ratio (CLR) and crack thickness ratio (CTR) are all zero.
  • CSR crack sensitivity ratio
  • CLR crack length ratio
  • CTR crack thickness ratio
  • the SSC resistance corresponds to the sulphide stress corrosion cracking resistance. This SSC resistance has been evaluated for each pipe (A1, 25.4mm), (A2, 25.4mm) (A3, 25.4mm), (A1, 15.9mm) and (A2, 15.9mm) according to the three following methods:
  • the pipes according to the present invention presented no failures and no secondary cracks across the section. All the pipes show an excellent sulphide stress cracking resistance and can therefore be used in severe sour conditions.
  • the steel composition (A1) according to the present invention has been prepared from the elements indicated in the table 1 above.
  • the steel (A1) thus obtained has then been hot formed according to the protocol previously mentioned in example 1 and the two following pipes (Ala) and (A1b) have been produced.
  • the pipe (A1b) After quenching and tempering, the pipe (A1b) has been aged and deformed according to the following protocol: The full wall strip specimen (A1b) has been submitted to uniaxial tensile stress causing a plastic deformation of 2% (A1b-2%) or of 5% (A1b-5%). The pipes have then been aged at 250°C for 1 hour. This protocol is intended to simulate the impact of reeling on the mechanical properties of the pipe at low temperatures.
  • the hardness behavior has been evaluated according to the standard ISO 6507-1, as previously mentioned in example 1.
  • This method is used to determine when the crack starts to propagate.
  • DNVGL-ST-F101 specification establishes a minimum CTOD value of 0.150 mm for the design temperature.
  • CTOD CTOD ⁇ Table 5 Steel T(°C) CTOD values (mm) notch 1 notch 2 notch 3 mean A1a -20°C 1.24 1.32 1.30 1.29 A1a -60°C 1.28 1.27 1.20 1.25 A1b-2% -60°C 1.19 1.28 1.20 1.23 A1b-5% -60°C 1.08 1.13 1.10 1.10
  • the SSC resistance has been evaluated for each pipes (A1a, 25.4mm), (A1a, 15.9mm) and (A1b-5%) according to the methods previously mentioned in example 1.
  • compositions of seamless pipe's steels according to the present invention (A4) and (A5) have been prepared from the elements indicated in the table 1 below, the amounts of which are expressed as percent by weight, relative to the total weight of the chemical composition.
  • Table 6 Steel A4 A5 Chemical composition (Unit: mass%, Balance: Fe and residual elements) c 0.071 0.062 Si 0.272 0.277 Mn 1.419 1.432 Cr 0.072 0.065 Mo 0.107 0.120 A1 0.029 0.025 N 0.0051 0.0072 Ni 0.168 0.18 V 0.040 0.045 Nb 0.0213 0.0209 Ti 0.0023 0.0052 P 0.007 0.009 s 0.0016 0.0023 B 0.0005 0.0004 Ca 0.0013 0.0012 Cu 0.029 0.05 Pcm 0.172 0.173 Ceq 0.364 0.381 C+Cr+Mo+Nb+V+Ti 0.2962 0.3136 Nb+V 0.0552 0.0613 Nb+V+Ti 0.0572 0.0636 Cr +
  • the steels (A4) and (A5) having the chemical compositions described in the table 6 above have been heated and then hot formed into seamless steel pipes of the desired dimensions by hot working using a rolling mill at 1250°C.
  • the seamless steel pipes thus obtained have a wall thickness (WT) equal to 25.4mm.
  • the seamless steel pipes After hot forming, the seamless steel pipes have undergone the following process conditions:
  • the hardness behavior has been evaluated according to the standard ISO 6507-1, according the method described for Example 1.
  • the tensile properties have been evaluated according to the standard ASTM A370.
  • each graph represents the yield strength values measured for each pipes (A4, 25.4mm) and (A5, 25.4mm).
  • CSR crack sensitivity ratio
  • CLR crack length ration
  • CTR crack thickness ratio
  • Pipes (A4, 25.4mm) and (A5, 25.4mm) passed the SSC test, corresponding to the test according to NACE TM0177-2016 Method A, with no failures and no secondary cracks after 720 hours. All the pipes showed an excellent sulphide stress cracking resistance and can therefore be used in severe sour conditions.
  • the steel composition (A4) and (A5) according to the present invention has been prepared from the elements indicated in the table 6 above.
  • the steel thus obtained has then been hot formed according to the protocol previously mentioned in example 2.
  • the pipe After quenching and tempering, the pipe has been aged and deformed according to the following protocol: an uniaxial tensile stress causing a plastic deformation of 5% was applied to the full wall pipe, and then the pipes have then been aged at 250°C for 1 hour.
  • the hardness behavior has been evaluated according to the standard ISO 6507-1, as previously mentioned in example 1.
  • CTOD CTOD ⁇ Table 8 Steel T(°C) CTOD values (mm) notch 1 notch 2 notch 3 mean A4 -20°C 1.35 1.36 1.34 1.35 A4 -60°C 1.23 1.20 1.27 1.23 A5 -60°C 1.31 1.38 1.32 1.33 A5 -60°C 1.24 1.18 1.21 1.21 A4-5% -20°C 1.22 1.18 1.15 1.18 A4-5% -60°C 1.02 1.08 1.11 1.07

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EP18195795.2A 2018-09-20 2018-09-20 High strength micro alloyed steel seamless pipe for sour service and high toughness applications Active EP3626841B1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP18195795.2A EP3626841B1 (en) 2018-09-20 2018-09-20 High strength micro alloyed steel seamless pipe for sour service and high toughness applications
ES18195795T ES2906376T3 (es) 2018-09-20 2018-09-20 Tubo sin costura de acero microaleado de alta resistencia para servicio en entornos ácidos y aplicaciones de alta tenacidad
PL18195795T PL3626841T3 (pl) 2018-09-20 2018-09-20 Rura bezszwowa z mikrostopowej stali o wysokiej wytrzymałości do zastosowań w warunkach kwaśnych i wysokiej wytrzymałości
AU2019222820A AU2019222820B2 (en) 2018-09-20 2019-08-27 High strength micro alloyed steel seamless pipe for sour service and high toughness applications
BR102019018917-7A BR102019018917B1 (pt) 2018-09-20 2019-09-12 Aço, tubo sem costura de aço e processo para fabricar um tubo sem costura
US16/572,918 US12276014B2 (en) 2018-09-20 2019-09-17 High strength micro alloyed steel seamless pipe for sour service and high toughness applications

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CN112391580A (zh) * 2020-11-09 2021-02-23 河钢股份有限公司承德分公司 一种钛强化500MPa级镀锌板热轧基料及生产方法
US20230416884A1 (en) * 2020-12-04 2023-12-28 ExxonMobil Technology and Engineering Company Linepipe Steel With Alternative Carbon Steel Compositions For Enhanced Sulfide Stress Cracking Resistance
JP7670004B2 (ja) * 2022-08-04 2025-04-30 Ｊｆｅスチール株式会社 ４０キロ級非調質型厚鋼板、溶接鋼管およびそれらの製造方法

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JPH0920961A (ja) * 1995-07-04 1997-01-21 Nippon Steel Corp 低温用シームレス鋼管の製造法
JP4792778B2 (ja) 2005-03-29 2011-10-12 住友金属工業株式会社 ラインパイプ用厚肉継目無鋼管の製造方法
MXPA05008339A (es) * 2005-08-04 2007-02-05 Tenaris Connections Ag Acero de alta resistencia para tubos de acero soldables y sin costura.
UA90948C2 (ru) * 2007-03-30 2010-06-10 Сумитомо Мэтал Индастриз, Лтд. Низколегированная сталь для нефтегазопромысловых труб (варианты) и бесшовная стальная труба
CN102154593B (zh) * 2011-05-26 2013-01-16 天津钢管集团股份有限公司 X80钢级抗腐蚀低温无缝管线管
JP6047947B2 (ja) * 2011-06-30 2016-12-21 Ｊｆｅスチール株式会社 耐サワー性に優れたラインパイプ用厚肉高強度継目無鋼管およびその製造方法
AU2013253775B2 (en) * 2012-04-27 2015-10-15 Nippon Steel Corporation Seamless steel pipe and method for producing the same
EP2789701A1 (en) * 2013-04-08 2014-10-15 DALMINE S.p.A. High strength medium wall quenched and tempered seamless steel pipes and related method for manufacturing said steel pipes
AR096272A1 (es) * 2013-05-31 2015-12-16 Nippon Steel & Sumitomo Metal Corp Tubo de acero sin costura para tubería de conducción utilizado en ambientes agrios
JP6572963B2 (ja) * 2017-12-25 2019-09-11 Ｊｆｅスチール株式会社 熱延鋼板およびその製造方法

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AU2019222820A1 (en) 2020-04-09
US12276014B2 (en) 2025-04-15
US20200095658A1 (en) 2020-03-26
PL3626841T3 (pl) 2022-04-04
BR102019018917A2 (pt) 2020-03-31
EP3626841A1 (en) 2020-03-25
AU2019222820B2 (en) 2025-01-30

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